Pulse radiolysis study of geminate recombination in charge transfer systems

1976 ◽  
Vol 80 (25) ◽  
pp. 2807-2810 ◽  
Author(s):  
Koichiro Hayashi ◽  
Dagmar Lindenau ◽  
Wolfram Schnabel ◽  
Masahiro Irie
1990 ◽  
Vol 68 (9) ◽  
pp. 918-924 ◽  
Author(s):  
Rolf E. Bühler

The semi-empirical rate law for geminate-ion recombination by van den Ende, Warman, and Hummel, which predicts a linear dependence of the ion concentration with t−0.6, is modified to include simultaneous ion fragmentation. The theory is applied to the kinetics, as observed by pulse radiolysis of liquid methylcyclohexane (MCH) solutions of N2O, CHCl3, or tert-butylchloride (t-BuCl) at low temperatures. In MCH saturated with N2O (−130 °C), the solvent cation (MCH+, λmax = 550 nm) moves about 400 times faster than prediced by diffusion. With the known conductivity data at room temperature, an activation energy of about 2.7 kJ/mol can be derived. The solvent cation MCH+ does not appear to fragment. With t-BuCl added to MCH (−134 °C), MCH+ (λmax = 550 nm) and t-BuCl− (λmax = 450 nm) are observed simultaneously. The initial kinetics corresponds to the parent ion (MCH+) recombination with t-BuCl−. Then the MCH+ fragmentation with k1(−134 °C) = 3 × 105 s−1 is observed, followed by the geminate recombination of some fragment cation with t-BuCl−. The fragment cation recombines 300 times slower than the parent cation. With CHCl3 added to MCH (−130 °C), the MCH+ absorption is hidden within the [Formula: see text] band (λmax = 470 nm); however, the fragmentation is detected from kinetic analysis to occur in about 2 × 106 s−1. The modified t−0.6 rate law appears to be a very useful tool to study simultaneous ion recombination and ion fragmentation.


2017 ◽  
Vol 19 (48) ◽  
pp. 32272-32285
Author(s):  
Hung-Cheng Chen ◽  
Andrew R. Cook ◽  
Sadayuki Asaoka ◽  
Jeffery S. Boschen ◽  
Theresa L. Windus ◽  
...  

Geminate recombination of 24 radical anions (M˙−) with solvated protons (RH2+) was studied in tetrahydrofuran (THF) with pulse radiolysis.


2021 ◽  
Vol 180 ◽  
pp. 109240
Author(s):  
John McGrady ◽  
Shinichi Yamashita ◽  
Sho Kano ◽  
Huilong Yang ◽  
Hiroaki Abe

Author(s):  
Aurélien de la Lande ◽  
Sergey A. Denisov ◽  
Mehran Mostafavi

The early mechanisms by which ionizing rays damage biological structure by so-called direct effect are largely elusive. In a recent picosecond pulse radiolysis study of concentrated uridine monophosphate solutions J. Phys. Chem. Lett.2018, 9, 5015]


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